Combustion synthesis of glass (Al2O3-CaO-X-Y) ceramic (TiB2) composites

ABSTRACT

The present invention is directed to the preparation of in-situ formation of a series of glass-ceramic composites by the Self-propagating High temperature Synthesis (SHS) technique with advantages of processing simplicity as well as the potential of cost savings. The materials produced by the technique contain crystalline TiB 2  phase and have either a pure glassy matrix or a glass matrix with partial devitrification based on the Al 2 O 3 —CaO system. The materials can potentially be used for infrared light transmission and for other high temperature applications. These materials can also be produced with relatively high porosity.

CROSS REFERENCE

[0001] This application is a continuation-in-part of application Ser. No. 09/591,902, filed Jun. 12, 2000.

BACKGROUND OF THE INVENTION

[0002] The present invention relates to the field of glass/ceramic composites and more particularly to glasses based on Al₂O₃—CaO which include TiB₂ phase.

[0003] It has long been found that alumininate glasses based on Al₂O₃ and CaO transmit infra-red light. Although there are other glasses which do this, (e.g., tellurites, germanates, etc.), the aluminates have a better combination of properties (optical, mechanical and thermal) as well as lower cost which makes them the attractive candidates when transmission out to about 6 μ is required. Glasses based on CaO—Al₂O₃ may be good candidates for this type of application since they are infrared light transmittable, have high softening temperature (>1000° C.) and good mechanical and thermal properties, and have lower costs compared to other similar materials Unfortunately, the CaO—Al₂O₃ system is readily devitrified and requires high critical cooling rate in order to form stable glass.

[0004] To promote glass formation, silica (SiO₂) has been added with some success. For instance, a composition of 48.6Al₂O₃-44.8CaO-6.6 SiO₂ (wt. %) was found to be devitrification free [see, J. E. Stanworth,, J. Soc. Glass Technol., 1948, vol. 32, pp. 154-172]. Glasses based on Al₂O₃-CaO without silica but with a complex composition were also produced [see, K. H. Sun, Glass Ind., 1949, vol. 30(4), pp.199-200, 232.]. Later on, silica free glasses with much simpler composition [e.g., 47Al₂O₃-43CaO-10BaO (wt. %)] were reported to be formed by Florence et al. [see, J. M., Florence, et al., J. Res. Natn. Bur. Stand., 1955, vol. 55, pp.231-237]. Finally, many glass compositions based on Al₂O₃-CaO and containing Na₂O, K₂O, MgO, BaO, La₂O₃ and Fe₂O₃ were produced by Hafner et al. [H. C. Hafner et al., J. Am Ceramic Soc., vol 41(8), 1958, pp.315-323]. However, these glasses were also devitrified to a different degree and pure glasses were obtained only after up to 5 mol % SiO₂ was added.

[0005] This invention uses a novel technique to produce glasses based on Al₂O₃-CaO with the possibility of lower costs than the traditional processing technique. The new glasses created in this invention have a simpler composition than those produced by Hafner et al. mentioned above. The glass matrix is based on Al₂O₃-CaO-BaO-SiO₂which contains higher A₂O₃ content and exhibits high softening temperature and better corrosion resistance. It also contains crystalline TiB₂ phase which appears as precipitates. The material can also be produced to contain relatively high porosity which finds use in applications requiring light weight and high temperature corrosion resistance.

[0006] The traditional technique of manufacturing Al₂O₃—CaO glasses involves fusion of the oxides at 1400-1500° C. for a long time followed by casting and shaping to desired shapes. On the other hand, this invention uses the Self-propagating High Temperature Synthesis (SHS) or Combustion Synthesis technique which is a favorable technique to produce glassy materials since the technique offers instant high combustion temperature without a furnace.

[0007] The application of the SHS technique to produce various crystalline materials has been demonstrated in many published articles and in a number of review articles [e.g., Moore and Feng, Progress in Materials Science, Vol. 39, 243-316 (1995); Munir and Anselmi-Tamburini, Materials Science Reports, vol.3, 277-365 (1989), Yi and Moore, J. Mater. Sci., vol. 25, 1159-1168 (1990)]. Simply speaking, the technique uses reactant powders to form a green pellet which is then ignited by an external heat source to generate chemical reactions, producing the end product in-situ. The SHS process can be realized by two modes, i.e., propagation (or combustion) mode and simultaneous (or thermal explosion) combustion mode. In the propagation mode, the reactants are ignited by an external heat source. Once ignited, the highly exothermic reaction ignites the next adjacent reactant layer by itself thereby generating a self-sustaining wave propagating toward the un-reacted part. In the simultaneous combustion mode, all the reactants are heated uniformly until the combustion reaction is initiated simultaneously throughout the whole pellet. A combustion synthesis reaction is defined by mainly three parameters: ignition temperature, which is the temperature at which the reaction rate becomes appreciable and self-sustaining; combustion temperature, which is the maximum temperature achieved; and combustion wave velocity, which is the overall combustion rate. However, the state of green reactants, (i.e. particle size, green density, reaction environment etc.) has a profound influence on the combustion synthesis process.

[0008] The present authors synthesized series of glass ceramic composites based on Al₂O₃—B₂O₃—BaO and Al₂O₃—B₂O₃—MgO glasses using the SHS technique (see Yi et al, U.S. Pat. No. 5,792,417 and Yi et al., U.S. Pat. application Ser. No. 09/351,227). The present invention is a further continuation in this work which reveals processing of another series of glass-ceramic composites based on CaO—Al₂O₃—X—Y. In these series X and Y can be any metal or any metal oxide. For purposes of this application, metal is defined to include Si. However in this document only examples of X and Y being SiO₂ and BaO are given.

[0009] Development of glass (Al₂O₃—CaO—X—Y) ceramic (TiB₂) composites and methods of synthesizing them represents a great improvement in the field of glasses and ceramics and satisfies a long felt need of the ceramic engineer.

SUMMARY OF THE INVENTION

[0010] This invention is a method for synthesising glass-ceramic composites, comprising the following steps:

[0011] b 1. mixing the reactant powders in proportion according to one of the following reactions:

3TiO₂+3B₂O₃+10Al+αCaO→3TiB₂+5Al₂O₃+αCaO+Q  (1)

3TiO₂+3B₂O₃+10Al+αCaO+βX→3TiB₂+5Al₂O₃+αCaO+βX+Q  (2)

3TiO₂+3B₂O₃10Al+αCaO+βX+γY→3TiB₂5Al₂O₃+αCaO+βX+γY+Q  (3)

TiH₂+B₂O₃+2Al+αCaO+βX+γY→TiB₂+Al₂O₃+αCaO+βX+γY+H₂(g)+Q  (4)

Ti+B₂O₃+2Al+αCaO+βX+γY→TiB₂+Al₂O₃αCaO+βX+γY+Q  (5)

[0012] where X and Y represent any metal oxide or any metal. For the purposes of this application metal is defined to include Si. It is desirable to limit the amount of silica to be added since it reduces the infrared transmission and heavier oxide such as BaO is preferred.

[0013] 2. pressing the mixed powders into pellets; and

[0014] 3. igniting the pellets in an argon atmosphere by resistant heating of a W-wire.

[0015] The glasses or partially devitrified glasses produced are based on the A₂O₃—CaO system and may contain one or more other substances resulting in A₂O₃—CaO—X—Y. The preferred composition of the products is Al₂O₃—CaO—BaO—SiO₂. The products also contain a ceramic phase, the ceramic phase being TiB₂. The preferred product has the following composition:

[0016] TiB₂: 13-26 wt. %

[0017] Al₂O₃: 29-50 wt. %

[0018] CaO: 16-42 wt. %

[0019] SiO₂: 0-35 wt. %

[0020] BaO: 0-17 wt. %.

[0021] An appreciation of the other aims and objectives of the present invention and an understanding of it may be achieved by referring to the accompanying drawings and description of a preferred embodiment.

BRIEF DESCRIPTION OF THE DRAWINGS

[0022]FIG. 1 is a graph of a typical temperature profile obtained during combustion synthesis of a sample having the composition 50Al₂O₃-30CaO-10SiO-10BaO.

[0023]FIG. 2 is a graph illustrating the effect of Al₂O₃ content on combustion characteristics.

[0024]FIG. 3 is a graph illustrating the effect of diluent content on combustion characteristics.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0025] The present invention uses powder reactants as raw materials. The powders are weighed according to the desired composition and thoroughly mixed by ball milling. Pellets with green densities (typically around 60% of theoretical) are pressed uniaxially. The final products were synthesized by igniting green pellets, thus establishing a self-propagating combustion reaction until the whole pellet is reacted. The combustion reactions were ignited by the propagation combustion mode. Pellets were ignited at one end in an inert atmosphere inside a chamber, and the combustion proceeded in a self-propagating way. The combustion temperatures (Tc) were measured by inserting C-type (5% W-Rh vs 26% W-Rh) thermocouples and wave velocities were measured by frame-by-frame analysis of a video recording of the combustion reaction. Microstructures were analysed by X-ray diffraction (XRD) and microscope.

[0026] Pellets could also be ignited by the simultaneous combustion mode, where a pellet was placed inside a furnace and heated to a certain temperature until combustion reactions are generated throughout of the whole sample. Combustion synthesis operations could also be carried out in air using other ignition techniques shown in our previous work (Yi et al., U.S. patent in application Ser. No. 09/351,227).

[0027] Binary CaO—Al₂O₃ with different compositions were first synthesized according to the following reaction:

3TiO₂+3B₂O₃+10Al++αCaO→3TiB₂+5Al₂O₃+αCaO+Q  (1)

[0028] The self-propagating combustion reaction is sustained by aluminum reducing TiO₂ and B₂O₃ at the combustion front thus releasing a large amount of heat (Q=612.4 kilo calorie) which is high enough to fuse the Al₂O₃ and CaO together forming a matrix comprising the two phases. The crystalline TiB₂ phase also exists in the product as a by-product (throughout document, the term matrix refers to the phases excluding the TiB₂ phase). By adjusting the coefficient a, binary CaO—Al₂O₃ system with different matrix compositions can be created. In the current work, compositions with different mass ratios of the two oxides were produced, with those containing higher aluminum oxide having higher combustion temperatures and wave velocities as expected. Unfortunately, none of these binary compositions formed pure glass matrices as will be shown later.

[0029] As mentioned before, glass formation may be promoted by adding another glass former such as SiO₂, or by adding another substance like BaO, or by adding both or more. To achieve this, the following reactions were conducted:

3TiO₂+3B₂O₃+10Al+αCaO+βX→3TiB₂+5Al₂O₃+αCaO+βX+Q  (2)

3TiO₂+3B₂O₃+10Al+αCaO+βX+γY→3TiB₂+5Al₂O₃+αCaOβX+γY+Q  (3)

[0030] X and Y can be any metal or metal oxide. For purposes of this application, metal is defined to include Si. In reaction (2), X (e.g., SiO₂, or BaO) is added to promote and stabilize the glass melt, while in reaction (3), both X (e.g., SiO₂) and Y (e.g., BaO) are added. The relative amounts of oxides in the glass matrix are adjusted by the coefficients α, β, and γ. Like CaO, the substances represented by X and Y act as diluents which reduce the combustion temperature and wave velocity. Therefore, there are maximum amounts of diluents that can be added without affecting self-propagating combustion reactions.

[0031] It was found that the combustion characteristics are greatly affected by the amount of diluent and by the amount of aluminium in the starting materials. Both the combustion temperature and wave velocity decreased with the increase of the amounts of diluents, and the opposite is true as the amount of aluminium oxide is increased. The latter was apparently caused by the increased exothermicity.

[0032] Microstructural analysis showed that none of the materials produced by reaction (1) formed substantial glass phase. However, those produced by reaction (2), i.e., Al₂O₃—CaO—SiO₂ system do form glass. As the amount of the SiO₂ increased, the glass phase also increased. It was also found that samples containing higher aluminum oxide favor glass formation, possibly due to higher combustion temperature associated with these combustion reactions. The combination of SiO₂ and BaO, as prepared by conducting reaction (3), also promoted glass formation. Materials with pure glass matrices have been formed in this system. All materials also contain the TiB₂ phase.

[0033] Typical apparent porosity (open pores) of the reacted samples was around <30% and overall porosity around 60% when samples were prepared using titanium dioxide as one of the reactants. In an effort to make these materials more porous, titanium hydride (TiH₂) was substituted for the titanium dioxide (TiO₂). For example, to produce porous Al₂O₃—CaO—SiO₂—BaO glass, the following reaction was carried out:

TiH₂+B₂O₃+2AlαCaO+βXγY→TiB₂+Al₂O₃+αCaO+βX+γY+H₂(g)+Q  (4)

[0034] The evolution of the hydrogen gas at the combustion front promoted formation of pores. The final reacted products contained apparent porosity of >40% and overall porosity of 60%. Exactly the same products can also be formed by substituting titanium dioxide in Reactions (1)-(3) by titanium. For instance, the glass matrix of Al₂O₃—CaO—SiO₂—BaO can also be produced by the following reaction:

Ti+B₂O₃+2Al+αCaO+βX+γY→TiB₂+Al₂O₃αCaO+βXγY+Q  (5)

[0035] Materials

[0036] Characteristics of the reaction powders are listed in Table 1. TABLE I Specifications of the Reactant Powders Reactant Particle Size, μm Impurity, % Al <44 <0.5 B₂O₃ <44 <0.02 CaO <44 <0.01 SiO₂ <44 <0.5 TiH₂ <44 <1 BaO <149 <0.5 Ti <44 <1

[0037] Examples of various matrix compositions in reacted products and the fractions of reactants to form them are given in Tables 2 and 3. The compositions are represented by weight (mass) percentage throughout this document unless specified otherwise. The matrix composition here is defined as the composition of the reacted product excluding TiB₂. For example, a composition represented by 50A₂O₃-30CaO-10SiO₂ -10BaO means the composition excluding TiB2 is 50wt. % Al₂O₃ -30wt. % CaO-10wt. % SiO₂ -10 wt. % BaO. The overall composition (including TiB₂ phase) of these materials is shown in Table 4.

[0038] Materials shown in Table 2 used TiO₂ as one of the reactants. However, in certain situations, porous glass materials may be desired. Therefore, titanium hydride (TiH₂) was used to replace titanium oxide to generate the same materials shown in the Table 2. Examples of selected materials with the same matrix composition are shown in Table 3. These materials produced using titanium hydride instead of titanium oxide contain higher porosity due to the evolution of hydrogen gas at the combustion front as shown in reaction (4). TABLE 2 Matrix Compositions (wt. %) of selected samples produced by the Combustion Reactions (1)-(3) and the weight percentage of Reactants to produce them Matrix Composition in Product (wt. %) alpha beta gamma TiO₂ B₂O₃ Al CaO SiO₂ BaO Reaction 50Al₂O₃-50CaO 9.1 0.0 0.0 19.5 17.0 22.0 41.5 0.0 0.0 1 45Al₂O₃-45CaO-10SiO₂ 9.1 1.9 0.0 17.9 15.6 20.1 38.0 8.4 0.0 2 40Al₂O₃-40CaO-20SiO₂ 9.1 4.2 0.0 16.2 14.1 18.2 34.4 17.2 0.0 2 40Al₂O₃-40CaO-10SiO₂-10BaO 9.1 2.1 0.8 16.2 14.1 18.2 34.4 8.6 8.6 3 47Al₂O₃-43CaO-10BaO 8.3 0.0 0.7 18.5 16.2 20.8 36.1 0.0 8.4 2 45Al₂O₃-35CaO-20SiO₂ 7.1 3.8 0.0 17.9 15.6 20.1 29.6 16.9 0.0 2 39.4Al₂O₃-30.6CaO-30SiO₂ 7.1 6.5 0.0 15.9 13.9 17.9 26.4 25.8 0.0 2 45Al₂O₃-35CaO-10SiO₂-10BaO 7.1 1.9 0.7 17.9 15.6 20.1 29.6 8.4 8.4 3 62.5Al₂O₃-37.5CaO 5.5 0 0 23.4 20.4 26.3 29.9 0.0 0.0 1 56.25Al₂O₃-33.75CaO-10SiO₂ 5.5 1.5 0.0 21.5 18.7 24.2 27.4 8.1 0.0 3 50Al₂O₃-30CaO-20SiO₂ 5.5 3.4 0.0 19.5 17.0 22.0 24.9 16.6 0.0 2 43.8Al₂O₃-26.2CaO-30SiO₂ 5.5 5.8 0.0 17.4 15.2 19.6 22.3 25.4 0.0 2 37.5Al₂O₃-22.5CaO-40SiO₂ 5.5 9.0 0.0 15.3 13.3 17.2 19.5 34.7 0.0 2 50Al₂O₃-30CaO-20BaO 5.5 0.0 1.3 19.5 17.0 22.0 24.9 0.0 16.6 2 50Al₂O₃-30CaO-5SiO₂-15BaO 5.5 0.8 1.0 19.5 17.0 22.0 24.9 4.2 12.5 3 50Al₂O₃-30CaO-10SiO₂-10BaO 5.5 1.7 0.7 19.5 17.0 22.0 24.9 8.3 8.3 3 50Al₂O₃-30CaO-15SiO₂-5BaO 5.5 2.5 0.3 19.5 17.0 22.0 24.9 12.5 4.2 3 50Al₂O₃-30CaO-17.5SiO₂-2.5BaO 5.5 3.0 0.2 19.5 17.0 22.0 24.9 14.5 2.1 3 45Al₂O₃-27CaO-20SiO₂-8BaO 5.5 3.8 0.6 17.9 15.6 20.1 22.8 16.9 6.8 3 41.7Al₂O₃-25CaO-20SiO₂-13.3BaO 5.4 4.1 1.1 16.7 14.6 18.9 21.4 17.1 11.4 3

[0039] TABLE 3 Matrix Compositions (wt. %) of selected samples produced by the Combustion Reactions (4) and the weight percentage of reactants to produce them Matrix Composition in Product (wt. %) alpha beta gamma TiH₂/Ti B₂O₃ Al CaO SiO₂ BaO Reaction 50Al₂O₃-30CaO-10SiO₂-10BaO 1.1 0.3 0.1 18.1 25.3 19.6 22.2 7.4 7.4 4 50Al₂O₃-30CaO-15SiO₂-5BaO 1.1 0.5 0.1 18.1 25.3 19.6 22.2 11.1 3.7 4 50Al₂O₃-30CaO-17.5SiO₂-2.5BaO 1.1 0.6 0.0 18.1 25.3 19.6 22.2 13.0 1.9 4 33.3Al₂O₃-20CaO-30SiO₂-16.7Ba0 1.1 1.5 0.3 13.2 18.4 14.3 16.2 24.3 13.5 4 37.5Al₂O₃-22.5CaO-40SiO₂ 1.1 1.8 0.0 14.5 20.3 15.7 17.8 31.7 0.0 4 50Al₂O₃-30CaO-10SiO₂-10BaO 1.1 0.3 0.1 17.5 25.5 19.7 22.4 7.5 7.5 5 50Al₂O₃-30CaO-15SiO₂-5BaO 1.1 0.5 0.1 17.5 25.5 19.7 22.4 11.2 3.7 5 50Al₂O₃-30CaO-17.5SiO₂-2.5BaO 1.1 0.6 0.0 17.5 25.5 19.7 22.4 13.1 1.9 5

[0040] TABLE 4 Overall Compositions (wt. %) of selected samples produced by the Reactions (1)-(4) Matrix Composition in Product (wt. %) TiB₂ Al₂O₃ CaO SiO₂ BaO Reaction 50Al₂O₃-50CaO 17.0 41.5 41.5 0.0 0.0 1 45Al₂O₃-45CaO-10SiO₂ 15.5 38.0 38.0 8.4 0.0 2 40Al₂O₃-40CaO-20SiO₂ 14.1 34.4 34.4 17.2 0.0 2 40Al₂O₃-40CaO-10SiO₂-10BaO 14.1 34.4 34.4 8.6 8.6 3 47Al₂O₃-43CaO-10BaO 16.1 39.4 36.1 0.0 8.4 2 45Al₂O₃-35CaO-20SiO₂ 15.5 38.0 29.6 16.9 0.0 2 39.4Al₂O₃-30.6CaO-30SiO₂ 13.9 33.9 26.4 25.8 0.0 2 45Al₂O₃-35CaO-10SiO₂-10BaO 15.5 38.0 29.6 8.4 8.4 3 62.5Al₂O₃-37.5CaO 20.4 49.8 29.9 0.0 0.0 1 56.25Al₂O₃-33.75CaO-10SiO₂ 18.7 45.7 27.4 8.1 0.0 2 50Al₂O₃-30CaO-20SiO₂ 17.0 41.5 24.9 16.6 0.0 2 43.8Al₂O₃-26.2CaO-30SiO₂ 15.2 37.1 22.3 25.4 0.0 2 37.5Al₂O₃-22.5CaO-40SiO₂ 13.3 32.5 19.5 34.7 0.0 2 50Al₂O₃-30CaO-20BaO 17.0 41.5 24.9 0.0 16.6 2 50Al₂O₃-30CaO-5SiO₂-15BaO 17.0 41.5 24.9 4.2 12.5 3 50Al₂O₃-30CaO-10SiO₂-10BaO 17.0 41.5 24.9 8.3 8.3 3 50Al₂O₃-30CaO-15SiO₂-5BaO 17.0 41.5 24.9 12.5 4.2 3 50Al₂O₃-30CaO-17.5SiO₂-2.5BaO 17.0 41.5 24.9 14.5 2.1 3 45Al₂O₃-27CaO-20SiO₂-8BaO 15.5 38.0 22.8 16.9 6.8 3 41.7Al₂O₃-25CaO-20SiO₂-13.3BaO 14.6 35.6 21.4 17.1 11.4 3 50Al₂O₃-30CaO-10SiO₂-10BaO 25.4 37.3 22.4 7.5 7.5 4 50Al₂O₃-30CaO-15SiO₂-5BaO 25.4 37.3 22.4 11.2 3.7 4 50Al₂O₃-30CaO-17.5SiO₂-2.5BaO 25.4 37.3 22.4 13.1 1.9 4 50Al₂O₃-30CaO-10SiO₂-10BaO 25.4 37.3 22.4 7.5 7.5 5 50Al₂O₃-30CaO-15SiO₂-5BaO 25.4 37.3 22.4 11.1 3.7 5 50Al₂O₃-30CaO-17.5SiO₂-2.5BaO 25.4 37.3 22.4 13.1 1.9 5

[0041] Experimental Procedures

[0042] Preparation started by weighing the reactant powders according to the desired compositions and thoroughly mixing them using ball milling dry in an inert atmosphere for at least 12 hours. Green pellets were then prepared by pressing the mixed powders uniaxially into density of approximately 60% of their theoretical densities. Green pellets were ignited by resistant heating a W-coil in an inert atmosphere inside a reaction chamber.

[0043] Ignition of the combustion reactions were realized by using an Xantrex power supply (model no XFR40-70, available from Xantrex Technology, Inc. of Burnaby, BC, Canada). The ignition power was controlled by computer and kept constant at 20V, 69A, 3 seconds for all of the samples. Temperature profiles during the combustion reactions were recorded by a data acquisition system using the DAQPad-1200 from National Instruments Corporation of Austin, Tex. Two C-type thermocouples (W-5% Re/W-26% Re) of 0.005 inches in diameter (welded under flowing argon atmosphere) were used. The thermocouple signals were conditioned and amplified by 5B series modules which were also from National Instruments. Finally, a video recording system consisting of a color camera with micro-zoom lens and a VCR was used to record the whole combustion process, from which the wave velocity was determined by frame-by-frame analysis of the wave front.

[0044] Combustion Characteristics

[0045] The ignition of these pellets was fairly easy and a self-propagating combustion wave was established in all samples. A typical temperature profile for a matrix composition of 50A₂O₃-30CaO-10SiO₂-10BaO (wt. %) that formed pure glass matrix (using reaction (3)) is shown in FIG. 1. The curve can be divided into three portions. The first portion (I) represents the temperature of the un-reacted part (room temperature), and the second portion (II) represents the sudden temperature rise to the maximum (combustion Temperature, Tc) when the combustion wave passed through the location of the thermocouples. A glass melt is formed at the combustion front. The third portion (III) represents the cooling process of the glass melt.

[0046] The relative amount of aluminum oxide, R (defined as the ratio of mass percentage of Al₂O₃ to that of CaO) in the matrix affects combustion characteristics substantially. This is illustrated in FIG. 2, where both the combustion temperature and wave velocity are plotted versus R for samples containing 20 wt. % SiO₂. The combustion temperatures increased from 1724 to 1919K, while the wave velocity increased from 1.1 to 3.1 mm/sec, as the R increased from 1.0 to 1.67 due to more heat being released. Undoubtedly, glass formation is also influenced substantially by combustion characteristics, particularly by the combustion temperature.

[0047] The combustion characteristics are also affected by the amount of diluents, as plotted in FIG. 3 for samples reacted for reaction (2). In this plot, the R value is kept constant at 1.67. The combustion temperature decreased from 2069K to 1773K while the wave velocity decreased from 4.1 mm/sec to 0.7 mm/sec, as the amount of silica increased from 0 to 40 wt. %.

[0048] As mentioned earlier, titanium hydride (TiH₂) can be used to substitute for titanium oxide (TiO₂) to produce exactly the same compositions using reaction (4). It was found that for the same composition produced using reaction (4), both the combustion temperatures and wave velocities were lower than these produced using reaction (3). Titanium (Ti) can also be used to substitute titanium oxide (TiO₂) to produce the same using reaction (5).

[0049] Combustion characteristics of selected compositions for all of the five reactions are summarized in Tables 5 and 6. TABLE 5 Combustion Temperature and Wave Velocity (average) for samples (represented by matrix composition) produced by Reactions (1)-(3) V, Matrix Composition (wt. %) Tc, K mm/s R Reaction 50 Al₂O₃-50 CaO 2108 4.1 1 1 45 Al₂O₃-45 CaO-10 SiO₂ 1706 1.7 1 2 40 Al₂O₃-40 CaO-20 SiO₂ 1724 0.96 1 2 40 Al₂O₃-40 CaO-10 SiO₂-10 BaO 1782 0.78 1 3 47 Al₂O₃-43 CaO-10 BaO 2013 2.2 1.09 2 45 Al₂O₃-35 CaO-20 SiO₂ 1847 2.2 1.29 2 39.4 Al₂O₃-30.6 CaO-30 SiO₂ 1809 0.9 1.29 2 45 Al₂O₃-35 CaO-10 SiO₂-10 BaO 1978 3.7 1.29 3 62.5 Al₂O₃-37.5 CaO 2069 4.1 1.67 1 56.25 Al₂O₃-33.75 CaO-10 SiO₂ 1870 3.7 1.67 2 50 Al₂O₃-30 CaO-20 SiO₂ 1944 3.1 1.67 2 43.8 Al₂O₃-26.2 CaO-30 SiO₂ 1850 1.3 1.67 2 37.5 Al₂O₃-22.5 CaO-40 SiO₂ 1773 0.7 1.67 2 50 Al₂O₃-30 CaO-20 BaO 2040 0.36 1.67 2 50 Al₂O₃-30 CaO-5 SiO₂-15 BaO 1958 0.32 1.67 3 50 Al₂O₃-30 CaO-10 SiO₂-10 BaO 1912 2.8 1.67 3 50 Al₂O₃-30 CaO-15 SiO₂-5 BaO 1950 1.6 1.67 3 50 Al₂O₃-30 CaO-17.5 SiO₂-2.5 BaO 1806 1.9 1.67 3 45 Al₂O₃-27 CaO-20 SiO₂-8 BaO 1916 2.1 1.67 3 41 Al₂O₃-25 CaO-20 SiO₂-13 BaO 1875 1.7 1.67 3

[0050] TABLE 6 Combustion Temperature and Wave Velocity (average) for sample (represented by matrix composition) produced by Reactions (1)-(3) V, Matrix Composition in Product (wt. %) Tc, K mm/s R Reaction 50 Al₂O₃-30 CaO-10 SiO₂-10 BaO 1959 1.8 1.67 4 50 Al₂O₃-30 CaO-15 SiO₂-5 BaO 1871 1.2 1.67 4 50 Al₂O₃-30 CaO-17.5 SiO₂-2.5 BaO 1602 1.5 1.67 4 2324 50 Al₂O₃-30 CaO-10 SiO₂-10 BaO 5.2 1.67 5 50 Al₂O₃-30 CaO-15 SiO₂-5 BaO 2229 4.8 1.67 5 50 Al₂O₃-30 CaO-17.5 SiO₂-2.5 BaO 2258 5.2 1.67 5

[0051] Glass Formation

[0052] The XRD and microscopic analysis results carried out are summarized in Table 7. The conventions used to describe the matrices in Table 7 are: pure glass indicating neither observable crystalline peaks on XRD patterns nor under microscope; mainly glass indicating small crystalline peaks on XRD patterns and/or small size sporadic crystalline phases observed under microscope; devitrified indicating appreciable amount of crystalline phases on the XRD and observable crystals in the glass matrix under microscope; and totally devitrified indicating mainly crystalline peaks on XRD and under microscope. All samples contain TiB2 phase which appears as crystalline precipitates.

[0053] Although the binary Al₂O₃—CaO system (near R=1) is a glass former [see H. Rawson, “inorganic glass-forming systems”, Academic Press, London and New York (1967)], the present work on two compositions, i.e., 50Al₂O₃-5CaO, 62.5Al₂O₃-37.5CaO showed that they do not form glasses at all. Full devitrification occurred throughout these samples most likely due to the fact that these compositions require a very high critical cooling rate to form glass.

[0054] In order to promote glass formation, different amounts of SiO₂ were first added to the Al₂O₃—CaO system while keeping the R value at 1. Up to 20% of SiO₂ was added, but no pure glass matrix was formed. Examination of an optical photomicrograph of a samples with a matrix composition of 45Al₂O₃-45CaO-10SiO₂ revealed that extensive devitrification had occurred in the glass matrix. However, as the amount of silica increases, less devitrification and more glass phase had been formed. This was clear from examination of a photomicrograph of a sample with a matrix composition of 40Al₂O₃-40CaO-20SiO₂. Therefore, it can be concluded that silica indeed promotes glass formation.

[0055] Next, the R value was increased to 1.29 and up to 30% SiO₂ was added. Both the combustion temperature and wave velocity were increased compared to the samples with an R value of 1 and the same amount of silica (see FIG. 2). More importantly, it was found that more glass phases were formed. For instance, the samples containing more than 20% SiO₂ formed a mainly glass matrix (matrix composition of 45Al₂O₃-35CaO-20SiO₂ and of 39.4Al₂O₃-30.6CaO-30SiO₂). Comparing an optical photomicrograph of the 45Al₂O₃-35CaO-20SiO₂ with optical photomicrographs of other compositions, one concludes that more aluminium oxide also promotes glass formation, possibly through raising of the combustion temperature.

[0056] Further raising the R value to 1.67 had similar results to that with the R value being 1.29. In this case, samples with 10% SiO₂ added (56.25Al₂O₃-33.75CaO-10SiO₂) formed pure glass matrices. However other crystalline phases other than the TiB₂ were also observed on XRD. Increasing the silica concentration to 20% (50Al₂O₃-30CaO-20SiO₂) resulted in a mainly glass matrix. However, as the amount of silica further increased to 30%(43.8Al₂O₃-26.2CaO-30SiO₂) and 40% (37.5Al₂O₃-22.5CaO-40SiO₂), even more devitrification occurred. A possible reason for this is that the combustion temperatures became too low.

[0057] In a work reported by Florence et al., a silica free sample with the composition of 47Al₂O₃-43CaO-10BaO was found to have formed glass. This work seems to suggest that BaO also promotes glass formation. Unfortunately, the samples with the same matrix composition done in the current work failed to form pure glass (devitrification occurred). This is a composition that has a R value of 1.09 and the combustion temperature was 2013K.

[0058] Further attempts were also made to partially replace silica with BaO. Samples with a matrix composition of 40Al₂O₃-40CaO-10SiO₂-10BaO (R=1) and of 45Al₂O₃-35CaO-10SiO₂-10BaO (R=1.29) still devitrified, but a pure glass matrix was obtained for samples with matrix composition of50Al₂O₃-30CaO-10SiO₂-10BaO, 50Al₂O₃-30CaO-15SiO₂-5BaO, 45Al₂O₃-27CaO-20SiO₂-8BaO, and 41Al₂ 0 ₃-25CaO-20SiO₂-13BaO (R=1.67). TiB₂ is the only crystalline phase in these samples. On the other hand, those samples with silica free composition (e.g., 47Al₂O₃-43CaO-10BaO, 50Al₂O₃-30CaO-20BaO) failed to produce pure glass matrices in the current work. Therefore, it appears that both BaO and SiO₂ are required to stabilize Al₂O₃—CaO glass melts.

[0059] The vitrification behavior of samples produced from reactions (4) and (5), i.e., using titanium hydride or titanium to replace titanium dioxide, were the same. For instance, the samples with a matrix composition of 50Al₂O₃-30CaO-10SiO₂-10BaO produced by both reaction also formed a pure glass matrix (see Table 7). TABLE 7 Microstructures of Reacted Samples R Matrix Compositions (wt. %) Matrix Reaction 1 50 Al₂O₃-50 CaO Totally 1 Devitrified 1 45 Al₂O₃-45 CaO-10 SiO₂ Devitrified 2 1 40 Al₂O₃-40 CaO-20 SiO₂ Devitrified 2 1 40 Al₂O₃-40 CaO-10 SiO₂-10 BaO Devitrified 3 1.09 47 Al₂O₃-43 CaO-10 BaO Devitrified 2 1.29 45 Al₂O₃-35 CaO-20 SiO₂ Mainly Glass 2 1.29 39.4 Al₂O₃-30.6 CaO-30 SiO₂ Mainly Glass 2 1.29 45 Al₂O₃-35 CaO-10 SiO₂-10 BaO Mainly Glass 3 1.67 62.5 Al₂O₃-37.5 CaO Totally 1 Devitrified 1.67 56.25 Al₂O₃-33.75 CaO-10 SiO₂ Pure Glass^(†) 2 1.67 50 Al₂O₃-30 CaO-20 SiO₂ Mainly Glass 2 1.67 43.8 Al₂O₃-26.2 CaO-30 SiO₂ Mainly Glass 2 1.67 37.5 Al₂O₃-22.5 CaO-40 SiO₂ Devitrified 2 1.67 50 Al₂O₃-30 CaO-20 BaO Devitrified 2 1.67 50 Al₂O₃-30 CaO-5 SiO₂-15 BaO Devitrified 3 1.67 50 Al₂O₃-30 CaO-10 SiO₂-10 BaO Pure Glass 3 1.67 50 Al₂O₃-30 CaO-15 SiO₂-5 BaO Pure Glass 3 1.67 50 Al₂O₃-30 CaO-17.5 SiO₂-2.5 BaO Mainly Glass 3 1.67 45 Al₂O₃-27 CaO-20 SiO₂-8 BaO Pure Glass 3 1.67 41.7 Al₂O₃-25 CaO-20 SiO₂-13.3 BaO Pure Glass 3 1.67 50 Al₂O₃-30 CaO-10 Si₂-10 BaO Pure Glass 4 1.67 50 Al₂O₃-30 CaO-15 SiO₂-5 BaO Pure Glass 4 1.67 50 Al₂O₃-30 CaO-17.5 SiO₂-2.5 BaO Mainly Glass 4 1.67 50 Al₂O₃-30 CaO-10 SiO₂-10 BaO Pure Glass 5 1.67 50 Al₂O₃-30 CaO-15 SiO₂-5 BaO Pure Glass 1.67 50 Al₂O₃-30 CaO-17.5 SiO₂-2.5 BaO Pure Glass 5

[0060] The morphology of the TiB₂ phase was also examined photomicrographically.

[0061] Porosity of the Products

[0062] Measurements on porosity of the reacted samples by the Archimedes method using water revealed that the overall porosity was around 60% (Table 8). Samples produced using reaction (4) had higher open and interconnected (apparent) pores than those produced by reaction (3). This is clearly caused by the evolution of the hydrogen gas generated in reaction (4). TABLE 8 Porosity of Samples Apparent Porosity Samples (%) (%) 50 Al₂O₃-30 CaO-10 SiO₂-10 BaO Reaction (3) 19 60 50 Al₂O₃-30 CaO-10 SiO₂-10 BaO Reaction (4) 39 60 50 Al₂O₃-30 CaO-15 SiO₂-5 BaO Reaction (3) 11 62 50 Al₂O₃-30 CaO-15 SiO₂-5 BaO Reaction (4) 42 60

EXAMPLE 1

[0063] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-50CaO for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of 60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 2108 K and the average wave velocity was 4.1 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of totally crystalline phases, in addition to the TiB₂ phase.

EXAMPLE 2

[0064] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 45A₂O₃-45CaO-10SiO₂ for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1842 K and the average wave velocity was 1. 7 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of a mixture of glass and crystalline phases, in addition to the TiB₂ phase.

EXAMPLE 3

[0065] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 40A₂O₃-40CaO-20SiO₂ for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1724 K and the average wave velocity was 1.1 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of a mixture of glass and crystalline phases, in addition to the TiB₂ phase.

EXAMPLE 4

[0066] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 40A₂O₃-40CaO-10SiO₂-10BaO for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1739 K and the average wave velocity was 1.5 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of a mixture of glass and crystalline phases, in addition to the TiB₂ phase.

EXAMPLE 5

[0067] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 47A₂O₃-43CaO-10BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 2013 K and the average wave velocity was 2.2 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of devitrified glass phases, in addition to the TiB₂ phase.

EXAMPLE 6

[0068] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 45A₂O₃-35CaO-20SiO₂ for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1847 K and the average wave velocity was 2.2 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of mainly glass phase, in addition to the TiB₂ phase.

EXAMPLE 7

[0069] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 39.4A₂O₃-30.6CaO-30SiO₂ for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1809 K and the average wave velocity was 0.9 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of mainly glass phase, in addition to the TiB₂ phase.

EXAMPLE 8

[0070] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 45A₂O₃-35CaO-10SiO₂-10BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1978 K and the average wave velocity was 3.7 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of mainly glass phase, in addition to the TiB₂ phase.

EXAMPLE 9

[0071] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 62.5A₂O₃-37.5CaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 2069 K and the average wave velocity was 4.1 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of totally crystalline phases, in addition to the TiB₂ phase.

EXAMPLE 10

[0072] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 56.25A₂O₃-33.75CaO-10SiO₂ for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1919 K and the average wave velocity was 3.7 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass, in addition to the TiB₂ phase, and other unknown crystalline phases.

EXAMPLE 11

[0073] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-20SiO₂ for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1944 K and the average wave velocity was 3.1 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of mainly glass phase, in addition to the TiB₂ phase.

EXAMPLE 12

[0074] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 43.8A₂O₃-26.2CaO-30SiO₂ for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of 60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1850 K and the average wave velocity was 1.3 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of mainly glass phase, in addition to the TiB₂ phase.

EXAMPLE 13

[0075] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 37.5A₂O₃-22.5CaO-20SiO₂ for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1773 K and the average wave velocity was 0.7 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of a mixture of glass and crystalline phases, in addition to the TiB₂ phase.

EXAMPLE 14

[0076] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-20BaO for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 2040K and the average wave velocity was 3.6 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of devitrified glass phases, in addition to the TiB₂ phase.

EXAMPLE 15

[0077] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-5SiO₂-15BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1958 K and the average wave velocity was 3.2 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of a mixture of glass and devitrified glass phases, in addition to the TiB₂ phase.

EXAMPLE 16

[0078] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-10SiO₂-10BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1912 K and the average wave velocity was 2.8 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase.

EXAMPLE 17

[0079] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-15SiO₂-5BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1950 K and the average wave velocity was 1.6 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase.

EXAMPLE 18

[0080] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-17.5SiO₂-2.5BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1806 K and the average wave velocity was 1.9 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of mainly glass phase with only very slight devitrification, in addition to the TiB₂ phase.

EXAMPLE 19

[0081] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 45A₂O₃-27CaO-20SiO₂-8BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1916 K and the average wave velocity was 2.1 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase.

EXAMPLE 20

[0082] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 41.7A₂O₃-25CaO-20SiO₂-13.3BaO for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1916 K and the average wave velocity was 2.1 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase. Examples 1-20 used titanium dioxide (rutile) as one of the reactants (reactions 1-3). The following examples used titanium hydride as one of the reactants (reaction 4).

EXAMPLE 21

[0083] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-10SiO₂-10BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of 60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1959 K and the average wave velocity was 1.8 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase. The average apparent porosity was 39% as compared to 19% for the same composition samples produced in Example 15.

EXAMPLE 22

[0084] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-15SiO₂-5BaO for at least 12 hours using ball milling . Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperature (Tc) was 1871 K and the average wave velocity was 1.2 mm/sec. X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase. The average apparent porosity was 42% as compared to 11% for the same composition samples produced in Example 16.

[0085] The following examples used titanium as one of the reactants (Reaction 5).

EXAMPLE 23

[0086] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-10SiO₂-10BaO for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperatures (Tc) were 2324 K and wave velocities were 5.2 mm/sec. The X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase.

EXAMPLE 24

[0087] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-15SiO₂-5BaO for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperatures (Tc) were 2229 K and wave velocities were 4.8 mm/sec. The X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase.

EXAMPLE 25

[0088] Reactant powders were dry mixed in proportions corresponding to a matrix composition of 50A₂O₃-30CaO-17.5SiO₂-2.5BaO for at least 12 hours using ball milling. Cylindrical pellets of 2.5 grams each were then pressed uniaxially to a green density of ˜60% of theoretical. The pellets were then ignited in a combustion chamber by resistant heating a W-coil under inert Argon atmosphere. The average combustion temperatures (Tc) were 2258 K and wave velocities were 5.2 mm/sec. The X-ray diffraction (XRD) on powders crushed from the reacted pellets and microscopic observation on polished samples showed that the matrix was composed of pure glass phase, in addition to the TiB₂ phase.

[0089] Combustion synthesis of glass (Al₂O₃—CaO—X) ceramic (TiB₂) composites has been described with reference to particular embodiments. Other modifications and enhancements can be made without departing from the spirit and scope of the claims that follow. 

What is claimed is:
 1. A process of making a glass-ceramic composite comprising the steps of: a. providing powdered T, B₂O₃, Al, CaO, X and Y, where T, X and Y are different, T is selected from the group consisting of Ti, TiO₂ and TiH₂, X is selected from the group consisting of metal and metal oxide and Y is selected from the group consisting of metal and metal oxide; b. weighing the powders in the following mole ratio: 3TiO₂, 3B₂O₃,10Al, αCaO, βX and γY if T is TiO₂ and T, B₂O₃, 2Al, αCaO, βX and γY if T is selected from the group consisting of Ti and TiH₂, where α,β and γ represent non-zero numbers; c. mixing the powders dry for adequate time in a ball mill; d. forming the mixed powders into a green pellet, uniaxially, to a density of about 60% theoretical; and e. igniting the pellet, whereby a reaction product having the formula 3TiB₂-5Al₂O₃-αCaO-βX-γY is produced if T is TiO₂ and a reaction product having the formula TiB₂-Al₂O₃-αCaO-βX-γY is produced if T is selected from the group consisting of Ti and TiH₂.
 2. A process of making a glass-ceramic composite as claimed in claim 1 in which the BaO powder has a particle sizes less than 44 μm and contains impurities less than 0.5% and all other powders have a particle size of less than 44 μm and contain impurities less than 1%.
 3. A process of making a glass-ceramic composite as claimed in claim 1 in which ignition is performed by resistance heating a W coil in an inert atmosphere inside a reaction chamber.
 4. A process of making a glass-ceramic composite as claimed in claim 1 in which ignition is performed by resistance heating a Kanthal-wire in air.
 5. A process of making a glass-ceramic composite as claimed in claim 1 in which ignition is performed by burning of a regular torch in air.
 6. A process of making a glass-ceramic composite as claimed in claim 1 in which ignition is performed by placing the pellets into a furnace previously heated to over 600° C.
 7. A process of making a glass-ceramic composite as claimed in claim 1 in which X is SiO₂ and Y is BaO.
 8. A process of making a glass-ceramic composite comprising the steps of: a. providing powdered TiO₂, B₂O₃, Al and CaO; b. weighing the powders in the following mole ratio: 3TiO₂, 3B₂O₃, 10Al, αCaO where α represents a non-zero number; c. mixing the powders dry for adequate time in a ball mill; d. forming the mixed powders into a green pellet, uniaxially, to a density of about 60% theoretical; and e. igniting the pellet, whereby a reaction product having the formula 3TiB2-5Al₂O₃-αCaO is produced.
 9. A process of making a glass-ceramic composite as claimed in claim 8 in which the powders have particle sizes less than 44 μm and contain less than 1 % impurities.
 10. A process of making a glass-ceramic composite as claimed in claim 8 in which ignition is performed by resistance heating a W coil in an inert atmosphere inside a reaction chamber.
 11. A process of making a glass-ceramic composite as claimed in claim 8 in which ignition is performed by resistance heating a Kanthal-wire in air.
 12. A process of making a glass-ceramic composite as claimed in claim 8 in which ignition is performed by burning of a regular torch in air.
 13. A process of making a glass-ceramic composite as claimed in claim 8 in which ignition is performed by placing the pellets into a furnace previously heated to over 600° C.
 14. A process of making a glass-ceramic composite as claimed in claim 8 further comprising the steps of: a. providing powdered X, which is selected from the group consisting of any metal and any metal oxide except TiO₂; and b. adding βX to the other powders prior to mixing; whereby said reaction product additionally contains βX.
 15. A process of making a glass-ceramic composite comprising the steps of: a. providing powdered TiO₂, B₂O₃, Al, CaO and X, where X is selected from the group consisting of any metal and any metal oxide except TiO₂; b. weighing the powders in the following mole ratio: 3TiO₂, 3B₂O₃, 10Al, αCaO, βX, where α and β represent non-zero numbers; c. mixing the powders dry for adequate time in a ball mill; d. forming the mixed powders into a green pellet, uniaxially, to a density of about 60% theoretical; and e. igniting the pellet, whereby a reaction product having the formula 3TiB₂-5Al₂O₃-αCaO-βX is produced.
 16. A process of making a glass-ceramic composite as claimed in claim 15 in which the powders have particle sizes less than 44 μm and contain less than 1% impurities.
 17. A process of making a glass-ceramic composite as claimed in claim 15 in which ignition is performed by resistance heating a W coil in an inert atmosphere inside a reaction chamber.
 18. A process of making a glass-ceramic composite as claimed in claim 15 in which ignition is performed by resistance heating a Kanthal-wire in air.
 19. A process of making a glass-ceramic composite as claimed in claim 15 in which ignition is performed by burning of a regular torch in air.
 20. A process of making a glass-ceramic composite as claimed in claim 15 in which ignition is performed by placing the pellets into a furnace previously heated to over 600° C.
 21. A process of making a glass-ceramic composite as claimed in claim 15 in which X is selected from the group consisting of SiO₂ and BaO. 